WO1995018176A1 - Composition expansible contenant un agent moussant chimique perfluore non sature - Google Patents

Composition expansible contenant un agent moussant chimique perfluore non sature Download PDF

Info

Publication number
WO1995018176A1
WO1995018176A1 PCT/US1994/013095 US9413095W WO9518176A1 WO 1995018176 A1 WO1995018176 A1 WO 1995018176A1 US 9413095 W US9413095 W US 9413095W WO 9518176 A1 WO9518176 A1 WO 9518176A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
blowing agent
foams
foamable
composition
Prior art date
Application number
PCT/US1994/013095
Other languages
English (en)
Inventor
Rudolf J. Dams
Richard M. Flynn
Koen Focquet
Alton J. Gasper
John G. Owens
Original Assignee
Minnesota Mining And Manufacturing Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to JP51801995A priority Critical patent/JP3419779B2/ja
Priority to EP95901889A priority patent/EP0737223A1/fr
Publication of WO1995018176A1 publication Critical patent/WO1995018176A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
    • C08J9/148—Halogen containing compounds containing carbon and halogen atoms only perfluorinated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143

Definitions

  • This invention relates to foamable compositions comprising fluorine-containing blowing agent compounds.
  • this invention relates to a process for preparing polymeric foams, e.g., polyurethane foams, to polymeric foams prepared from the foamable compositions, and to articles comprising the foams.
  • CFCs Chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • HFCs hydrofluorocarbons
  • U.S. Pat. No. 5,162,384 (Owens et al.) describes a blowing agent emulsion comprising at least one low boiling, perfluorinated, N-aliphatic, cyclic 1,3- or 1,4-aminoether.
  • EP 439,283 (BP Chemicals Limited) discloses blowing agents comprising perfluoro- or partially fluorinated-(cyclo)alkanes.
  • EP 416,777 (Imperial Chemical Industries) describes a method for the preparation of a polymeric foam which comprises vaporising a fluorine-containing ether in the presence of a foamable polymer or the precursors of a foamable polymer.
  • CA 2,037, 587 (Hoechst Aktiengesellschaft) describes a process for the manufacture of foams with the aid of blowing agents containing fluoroalkanes and fluorinated ethers.
  • U.S. Pat. No. 4,972,003 discloses a blowing agent composition comprising one or more organic compounds, particularly halocarbons, having a boiling point of less than or equal to 272K at atmospheric pressure, which composition is substantially free of organic compounds having a boiling point of 273K or greater.
  • U.S. Pat. No. 5,205,956 discloses a process for the production of plastic foams, in which the blowing agent used is at least one vinylfluoroalkane.
  • Japanese Patent Publication Nos. 51-79042, 51-79043, and 51-79045 disclose the use of 2-trifluoromethyl-3,3,3-trifluoro-l-propene, cis-l,l,l,4,4,4-hexafluoro-2-butene, and 4-hydro- heptafluoro-l-butene, respectively, as foaming agents.
  • this invention provides foamable compositions for use in preparing polymeric, e.g., polyurethane, foams.
  • the compositions comprise (a) at least one normally liquid, unsaturated perfluorochemical blowing agent compound selected from the group consisting of perfluoroolefin compounds, e.g., perfluoro(4-methylpent-2-ene) , perfluoroaromatic compounds, e.g., hexafluorobenzene, and perfluorocycloolefin compounds, e.g., perfluorocyclohexene, the perfluoroolefin compounds optionally containing one or more catenary, i.e., in- chain, heteroatoms; and (b) at least one foamable polymer or the precursors of at least one foamable polymer.
  • perfluoroolefin compounds e.g., perfluoro(4-methylpent-2-ene)
  • perfluoroaromatic compounds e.
  • the term "normally liquid” means liquid under ambient conditions.
  • the blowing agent compound has a boiling point greater than or equal to about 20°C.
  • Reactive components which react with one another either during or after foaming to form a foamable polymer are regarded herein as precursors of a foamable polymer.
  • Perfluoroolefins and perfluorocycloolefins are preferred blowing agent compounds due to considerations of cost and availability.
  • the foamable compositions of the invention comprising unsaturated perfluorochemical as blowing (or co-blowing) agent generally provide polymeric foams having a smaller cell size (and therefore better insulation efficiency) than foams produced using only conventional blowing agents such as CFCs, HCFCs, HFCs, hydrocarbons, hydrochlorocarbons, or water.
  • the compositions of the invention are also more "environmentally friendly" than compositions containing some conventional blowing agents, e.g., CFCs and HCFCs, as the unsaturated perfluorochemical blowing agent compounds utilized in the compositions have an ozone depletion potential of zero.
  • the compounds also advantageously have shorter atmospheric lifetimes (due to their greater reactivity) than saturated perfluorochemical blowing agents, and thus have lower global warming potentials.
  • unsaturated perfluorochemical blowing agent compounds are known to be highly reactive toward nucleophiles such as alcohols in the presence of basic catalysts such as trialkylamines (see, e.g., Organofluorine Chemicals and their Industrial Applications edited by R. E. Banks, pages 29-32, Ellis Horwood Ltd., Chichester (1979) ; Advances in Fluorine Chemistry. Volume 4 edited by M. Stacey, J. C.
  • the apparently latent reactivity of the unsaturated perfluorochemical blowing agents can potentially be utilized to advantage later in the foam- blowing process to chemically "anchor" the blowing agent in the foam to prevent its diffusion and release into the atmosphere, thereby further reducing environmental concerns.
  • this invention provides a process for preparing polymeric foams, polymeric foams prepared from the foamable compositions of the invention, and articles comprising the foams.
  • the foams can vary in texture from very soft types useful in upholstery applications to rigid foams useful as structural or insulating materials.
  • Unsaturated perfluorochemical blowing agent compounds suitable for use in the foamable compositions of the invention are normally liquid perfluoroolefin compounds, perfluoroaromatic compounds, and perfluorocycloolefin compounds.
  • the compounds can contain some residual carbon-bonded hydrogen (generally less than about 0.4 mg/g and preferably less than about 0.1 mg/g, e.g., 0.01 to 0.05 mg/g) but are preferably substantially completely fluorinated.
  • the perfluoroolefin compounds can contain one or more catenary heteroatoms, e.g., nitrogen or oxygen atoms.
  • blowing agent compounds include hexafluoropropene dimers, e.g., perfluoro(4-methylpent-2-ene) and perfluoro(2- methylpent-2-ene) ; hexafluoropropene trimers, e.g., perfluoro(4-methyl-3-isopropylpent-2-ene) and perfluoro(2,4-dimethyl-3-ethylpent-2-ene) ; tetrafluoroethylene oligomers, e.g., perfluoro(3- methylpent-2-ene) , perfluoro(3,4-dimethylhex-3-ene) , and perfluoro(2,4-dimethyl-4-ethylhex-2-ene) ; perfluoro(l-pentene) ; perfluoro(2-pentene) ; perfluoro(1-hexene) ; perfluor
  • the unsaturated perfluorochemical blowing agent compounds preferably have boiling points greater than or equal to about 20°C. More preferably, the compounds have boiling points in the range of from about 45°C to about 125°C. Compounds having such boiling points are well-suited for foam blowing at atmospheric pressure.
  • Perfluoroolefins and perfluorocycloolefins are preferably utilized in the compositions of the invention due to considerations of cost and availability. More preferably, perfluoroolefins are utilized because of the wide range of boiling points available.
  • Perfluoroolefin compounds (as well as catenary heteroatom-containing perfluoroolefin compounds) suitable for use in the foamable compositions of the invention can be prepared by methods such as the decarboxylation of salts of fluorocarboxylie acids (see, e.g., A. M. Lovelace, D. A. Rausch, and W. Postelnek, Aliphatic Fluorine Compounds. Chapter III (Alkenes and Alkynes) , pages 107-09, Reinhold Publishing Corporation, New York (1958)) and the coupling of two or more perfluoroolefins (as described, e.g., in U.S. Pat. No.
  • Hexafluoropropene oligomers can be prepared by various gas-phase and liquid-phase methods such as those described in, e.g., U.S. Pat. No. 5,254,774 (Prokop) . Hexafluoropropene dimer and a mixture of hexafluoropropene trimers are also commercially available (e.g., from Fluorochem Limited). Tetrafluoroethylene oligomers can be prepared by methods such as those described in, e.g., U.S. Pat. Nos.
  • Perfluorocycloolefin compounds suitable for use in the foamable compositions of the invention can be prepared by the electrochemical fluorination of aromatic acid derivatives followed by decarboxylation, as described for perfluorocyclohexene by G. Gambaretto and G. Troilo in Chim. Ind. 51(11), 1097-102 (1970) and Ann. Chim. 59.(8-9), 690-701 (1969). See also Chambers, supra. In addition, see U.S. Pat. No. 3,331,880 (Anello et al.) which describes methods for preparing polyfluorocyclohexenes.
  • Perfluorocyclohexene is also commercially available (e.g., from Fluorochem Limited).
  • Perfluoroaromatic compounds suitable for use in the foamable compositions of the invention can be prepared by various methods (such as the defluorination of perfluorocycloalkanes) described, e.g., in Chambers, supra f pages 261-73.
  • Hexafluorobenzene is commercially available (e.g., from Fluorochem Limited).
  • the unsaturated perfluorochemical blowing agents can be used alone as the sole blowing agent in the foamable composition or can be used in combination with saturated perfluorochemical blowing agents or with conventional blowing agents, e.g., CFCs, HCFCs, HFCs, hydrocarbons, hydrochlorocarbons (HCCs) , or water. Mixtures of unsaturated perfluorochemical and other blowing agent(s) are generally preferred due to cost considerations.
  • suitable co-blowing agents include hydrocarbons, e.g., pentane, hexane, and cyclopentane; halohydrocarbons, e.g., 1,1-dichloro-l-fluoroethane, 1,l-dichloro-2,2,2- trifluoroethane, 1-hydropentadecafluoroheptane, 1,1,1,2-tetrafluoroethane, chlorodifluoro ethane, 1- chloro-1,1-difluoroethane, and 2-chloropropane; chlorofluorocarbons, e.g., fluorotrichloromethane; water (which reacts with isocyanate to produce carbon dioxide); saturated perfluorochemicals, e.g., perfluoropentane, perfluorohexane, and perfluoro(N- methylmorpholine) ; and mixtures thereof.
  • hydrocarbons e.g., pen
  • co- blowing agents are normally liquid blowing agent compounds, e.g., 1,1-dichloro-l-fluoroethane, cyclopentane, pentane, hexane, water, and perfluoro(N- methylmorpholine) .
  • co-blowing agent can generally be utilized in an amount in the range of from about 0.5 to about 99.5 weight percent (preferably, from about 40 to about 95 weight percent, more preferably from about 75 to about 90 weight percent) of the blowing agent mixture.
  • Foamable polymers suitable for use in the foamable compositions of the invention include polyolefins, e.g., polystyrene, poly(vinyl chloride), and polyethylene. Foams can be prepared from styrene polymers using conventional extrusion methods. The blowing agent(s) can be injected into a heat-plastified styrene polymer stream within an extruder and admixed therewith prior to extrusion to form foam.
  • Suitable styrene polymers include the solid homopolymers of styrene, ⁇ - methylstyrene, ring-alkylated styrenes, and ring- halogenated styrenes, as well as copolymers of these monomers with minor amounts of other readily co- polymerizable olefinic monomers, e.g., methyl methacrylate, acrylonitrile, maleic anhydride, citraconic anhydride, itaconic anhydride, acrylic acid, N-vinylcarbazole, butadiene, and divinylbenzene.
  • Suitable vinyl chloride polymers include vinyl chloride homopolymer and copolymers of vinyl chloride with other vinyl monomers. Ethylene homopolymers and copolymers of ethylene with, e.g., 2-butene, acrylic acid, propylene, or butadiene are also useful. Mixtures of different types of polymers can be employed.
  • Precursors of foamable polymers suitable for use in the foamable compositions of the invention include precursors of phenolic polymers, silicone polymers, and isocyanate-based polymers, e.g., polyurethane, polyisocyanurate, polyurea, polycarbodiimide, and polyimide.
  • preferred foamable compositions of the invention comprise (a) at least one normally liquid blowing agent compound selected from the group consisting of perfluoroolefin compounds, perfluoroaromatic compounds, and perfluorocycloolefin compounds, the perfluoroolefin compounds optionally containing one or more catenary heteroatoms; (b) at least one organic polyisocyanate; and (c) at least one compound containing at least two reactive hydrogen atoms.
  • Polyisocyanates suitable for use in the preferred compositions of the invention include aliphatic, alicyclic, arylaliphatic, aromatic, or heterocyclic polyisocyanates, or combinations thereof. Any polyisocyanate which is suitable for use in the production of polymeric foams can be utilized. Of particular importance are aromatic diisocyanates such as toluene and diphenylmethane diisocyanates in pure, modified, or crude form.
  • MDI variants diphenylmethane diisocyanate modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine, or isocyanurate residues
  • crude or polymeric MDI polymethylene polyphenylene polyisocyanates
  • suitable polyisocyanates include ethylene diisocyanate, 1,4- tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3- diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate (and mixtures of these isomers), diisocyanato-3,3,5- trimethyl-5-isocyanatomethyl cyclohexane, 2,4- and 2,6- toluene diisocyanate (and mixtures of these isomers) , diphenylmethane-2,4 '- and/or -4,4'-diisocyanate, naphthalene-l,5-diisocyanate, the reaction products of four equivalents of the aforementioned isocyanate- containing compounds with compounds containing two isocyanate,
  • Distillation residues (obtained in the commercial production of isocyanates) having isocyanate groups can also be used alone or in solution in one or more of the above- mentioned polyisocyanates.
  • Reactive hydrogen-containing compounds suitable for use in the preferred foamable compositions of the invention are those having at least two isocyanate-reactive hydrogen atoms, preferably in the form of hydroxy1, primary or secondary amine, carboxylic acid, or thiol groups, or a combination thereof.
  • Polyols, i.e., compounds having at least two hydroxyl groups per molecule, are especially preferred due to their desirable reactivity with polyisocyanates.
  • Preferred polyols are those having from 2 to about 50, preferably from 2 to about 8, more preferably from 2 to about 4, hydroxyl groups.
  • Such polyols can be, e.g., polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polymethacrylates, polyester amides, or hydroxyl-containing prepolymers of these compounds and a less than stoichiometric amount of polyisocyanate.
  • the reactive hydrogen-containing compounds utilized in the preferred foamable compositions of the invention have a weight average molecular weight of from about 50 to about 50,000, preferably from about 500 to about 25,000.
  • Useful polyols include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3- butylene glycol, 1,5-pentane diol, 1,6-hexane diol, 1,8-octane diol, neopentyl glycol, 1,4- bis(hydroxymethyl)cyclohexane, 2-methyl-l,3-propane diol, dibromobutene diol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, higher polyethylene glycols, dipropylene glycol, higher polypropylene glycols, dibutylene glycol, higher polybutylene glycols, 4,4'-dihydroxydiphenyl propane, and dihydroxyme
  • suitable polyols include the condensation products of polybasic acids and polyols such as polyethylene adipate and polycaprolactone-based polyols, as well as the mixtures of hydroxy aldehydes and hydroxy ketones (“formose”) and the polyhydric alcohols obtained therefrom by reduction (“formitol”) that are formed in the autocondensation of formaldehyde hydrate in the presence of metal compounds as catalysts and compounds capable of enediol formation as co-catalysts (see, e.g., U.S. Pat. Nos.
  • polymeric foams can be prepared using the foamable compositions of the invention by vaporizing at least one normally liquid, unsaturated perfluorochemical blowing agent compound selected from the group consisting of perfluoroolefin compounds, perfluoroaromatic compounds, and perfluorocycloolefin compounds, the perfluoroolefin compounds optionally containing one or more catenary heteroatoms, in the presence of at least one foamable polymer or the precursors of at least one foamable polymer.
  • perfluoroolefin compounds selected from the group consisting of perfluoroolefin compounds, perfluoroaromatic compounds, and perfluorocycloolefin compounds, the perfluoroolefin compounds optionally containing one or more catenary heteroatoms
  • blowing agent compound or mixture of blowing agent compounds, which may contain co-blowing agent
  • the amount of blowing agent compound (or mixture of blowing agent compounds, which may contain co-blowing agent) utilized is preferably up to about 30% by weight of the foamable composition
  • Polymeric foams can be prepared using the preferred foamable compositions of the invention by vaporizing (e.g., by utilizing the heat of precursor reaction) at least one normally liquid, unsaturated perfluorochemical blowing agent compound in the presence of at least one organic polyisocyanate and at least one compound containing at least two reactive hydrogen atoms.
  • from about 0.1 to about 50 parts by weight of blowing agent compound(s) is used in combination with from about 100 to about 300 parts by weight of polyisocyanate(s) and from about 100 to about 150 parts by weight of reactive hydrogen-containing compound(s) .
  • the polyisocyanate, reactive hydrogen-containing compound, and blowing agent can generally be combined, thoroughly mixed (using, e.g., any of the various known types of mixing head and spray apparatus) , and permitted to expand and cure into a cellular polymer. It is often convenient, but not necessary, to preblend certain of the components of the foamable composition prior to reaction of the polyisocyanate and the reactive hydrogen-containing compound. For example, it is often useful to first blend the reactive hydrogen- containing compound, blowing agent, and any other components (e.g., surfactant) except the polyisocyanate, and to then combine the resulting mixture with the polyisocyanate. Alternatively, all components of the foamable composition can be introduced separately. It is also possible to pre- react all or a portion of the reactive hydrogen- containing compound with the polyisocyanate to form a prepolymer.
  • foam formulations can optionally be present in the foamable compositions of the invention.
  • foam-stabilizing agents or surfactants can be utilized.
  • catalysts can be utilized.
  • blowing agents or blowing agent precursor compounds
  • Other possible components include cell regulators, fillers, colorants, fungicides, bactericides, antioxidants, reinforcing agents, antistatic agents, and other additives or processing aids known to those skilled in the art.
  • the foamable compositions of the invention include at least one surfactant.
  • Suitable surfactants include fluorochemical surfactants, organosilicone surfactants, polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonate esters, alkyl arylsulfonic acids, fatty acid alkoxylates, and mixtures thereof.
  • Surfactant is generally employed in amounts sufficient to stablilize the foaming reaction mixture against collapse and the formation of large, uneven cells. Typically, from about 0.1 to about 5 percent by weight of surfactant is sufficient for this purpose.
  • Organosilicone surfactants and fluorochemical surfactants are preferred.
  • the preferred foamable compositions of the invention which are useful in preparing isocyanate- based foams often advantageously contain cross-linking and/or chain-extending agents to modify the mechanical properties of the resulting foams, as well as catalysts to increase the rate of reaction of the components of the composition.
  • Suitable cross-linking or chain- extending agents include aliphatic, alicyclic, and arylaliphatic polyols and polyamines having a molecular weight of less than about 400 and preferably containing from about 2 to about 20 carbon atoms.
  • suitable polyols include ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, and p- dihydroxycyclohexane, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, bis(2- hydroxyethyl)hydroquinone, 1,2,4- and 1,3,5- trihydroxycyclohexane, glycerol, trimethylolpropane, low molecular weight hydroxyl group-containing polyalkylene oxides based on ethylene oxide and 1,2- propylene oxide, and mixtures thereof.
  • cross-linking or chain-extending agents include polyamines such as primary aromatic diamines, secondary aromatic diamines, and 3,3 , -di- or 3,3',5,5'- tetraalkyl-substituted diaminodiphenylmethanes.
  • the cross-linking and chain-extending agents can be used individually or as mixtures and, when used, can generally be present in amounts ranging from about 2 to about 60 weight percent of the foamable composition.
  • Catalysts suitable for use in the preferred foamable compositions of the invention include compounds which greatly accelerate the reaction of the reactive hydrogen-containing compounds (or the cross- linking or chain-extending agents) with the polyisocyanates. When used, catalysts are generally present in amounts sufficient to be catalytically effective.
  • Suitable catalysts include organic metal compounds (preferably, organic tin compounds) , which can be used alone or, preferably, in combination with strongly basic amines. Representative examples of these and other types of suitable catalysts are described in U.S. Pat. No. 4,972,002 (Volkert) .
  • Foams prepared from the foamable compositions of the invention can vary in texture from very soft types useful in upholstery applications to rigid foams useful as structural or insulating materials.
  • the foams can be used, for example, in the automobile, shipbuilding, aircraft, furniture, and athletic equipment industries, and are especially useful as insulation materials in the construction and refrigeration industries.
  • the thermal conductivity (lambda) values of the resulting foams were measured on a Hesto Lambda Control A50-A thermal conductivity analyzer with a reproducibility of +/- 0.1.
  • the comparative cell sizes described in the examples are designated as follows:
  • HFP hexafluoropropene dimer
  • Hoechst AG believed to be predominately perfluoro(4-methylpent-2- ene)
  • HFP dimer hexafluoropropene dimer dimer
  • a polymeric polyether polyol having a hydroxy equivalent weight of 425 milligrams KOH/gram, a viscosity of 820 cp, a water content of 4.6 pbw, and a catalyst content of 3.7 pbw of N,N-dimethylcyclohexyl amine
  • this polyol is commercially available as BaythermTM VP-PU 1751A/2 from Bayer A.G.
  • silicone surfactant available as B-8423 from T.H.
  • the thermal conductivity of a section of the foam was measured as described above and found to be 22.3 mW[m(K)]"' initially and 30.7 mWtm(K)]" 1 after two weeks of aging at 50°C.
  • a polyurethane foam was prepared essentially according to the procedure of Example 1 (the components and their amounts are given in Table 1) except that 3.5 pbw of an oligomeric fluorochemical surfactant (described in Example 1 of U.S. Pat. No. 3,787,351 (Olson) (hereinafter, '351)) was substituted for the silicone surfactant.
  • the density, cell size, and thermal conductivity data for the resulting foam are shown in Table 1.
  • Polyurethane foams were prepared essentially according to the procedure of Example 1, using the components and amounts listed in Table 1.
  • the C 6 F, 0 (perfluorocyclohexene) utilized in Examples 7 and 8 was purchased from Fluorochem Limited (United Kingdom) and is available as F05931.
  • the tetrafluoroethylene (TFE) oligomer utilized in Examples 3 and 4 was purchased from ICI (United Kingdom) and is believed to be a mixture of tetramer, pentamer, and hexamer.
  • the density, cell size, and thermal conductivity data for the resulting foams are shown in Table 1.
  • a polyurethane foam was prepared essentially according to the procedure of Example 1 (the components and their amounts are given in Table 1) but without the addition of HFP dimer. The density, cell size, and thermal conductivity data for the resulting foam are shown in Table 1.
  • Example 2 A polyurethane foam was prepared essentially as in Example 2 (the components and their amounts are given in Table 1) but without the addition of HFP dimer. The density, cell size, and thermal conductivity data for the resulting foam are shown in Table 1.
  • Isocyanate 44V20 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227 227
  • CF,OCF CF 2 (Perfluoro(3- 3.5 3.5 oxahe ⁇ t-1-ene) )
  • Polyurethane foams were prepared essentially as in Example 2, using the components and amounts listed in Table 2.
  • the polymeric polyether polyol utilized had an average molecular weight of 630, a viscosity of about 2000 cp, and a hydroxy content of about 6 hydroxyl groups per molecule.
  • the polyol can be prepared by the reaction of sorbitol with propylene oxide and is commercially available from ICI as Polyol ICI-C.
  • the isocyanate utilized (Dow Chemical Company's PAPITM 135) was a polymeric methylene diphenyldiisocyanate having an isocyanate equivalent of 132.
  • PAPITM 135 is no longer available from Dow and has been replaced by PAPITM 27, an equivalent product having less color.
  • Example 12 The HFP trimer utilized in Example 12 was purchased from Hoechst AG and is believed to be a mixture of predominately perfluoro(4-methy1-3- isopropylpent-2-ene) and perfluoro(2,4-dimethyl-3- ethylpent-2-ene) .
  • the thermal conductivity data for the resulting foams is shown in Table 2.
  • Polyurethane foam was prepared essentially as in Example 2 , using the components and amounts listed in Table 2 for Example 12, except that no water was added and 90 pbw of HFP trimer was utilized.
  • the thermal conductivity of a section of the foam was measured as described above and found to be 22.0 mWIXK)] "1 initially and 25.8 mWIXK)]- 1 after one week of aging at 70°C. Comparative Examples C, D. E. and F
  • Polyurethane foams were prepared essentially as in Examples 11 and 12 (using the components and amounts listed in Table 2) except that various conventional blowing agents were substituted for the perfluoroolefin compounds.
  • the polyol used in Comparative Example E was Polyol Bayer PU 1732, having a viscosity of about 1200 cp and a hydroxy equivalent weight of about 400 mg KOH/g.
  • the thermal conductivity data for the resulting foams is shown in Table 2.
  • foamable compositions of the present invention comprising unsaturated perfluorochemical blowing agent compound can produce foams having conductivities superior or equivalent to those of foams blown with conventional blowing agents.
  • the compositions thus provide alternatives to the use of blowing agents which deplete atmospheric ozone (such as l,l-dichloro-2,2,2-trifluoroethane) or which are flammable (such as cyclopentane) .
  • Polyurethane foams were prepared essentially according to the procedure of Example 1, using the components and amounts listed in Table 3.
  • Polyol 1832 A/2 commercially available from Bayer AG as BaythermTM VP-PU 1832 A/2, is a polyether polyol having a hydroxy equivalent weight of 520 mg KOH/g, a water content of about 1.9 pbw, a catalyst content of 3.7 pbw of N,N- dimethylcyclohexyl amine, and a viscosity of about 4000 cp.
  • 1,1-Dichloro-l-fluoroethane available from both Atochem and Allied-Signal was used in each case as a co-blowing agent.
  • the density, cell size, and thermal conductivity data for the resulting foams are shown in Table 3.
  • a polyurethane foam was prepared essentially as in Examples 13-16 (the components and their amounts are given in Table 3) but without the addition of unsaturated perfluorochemical.
  • the density, cell size, and thermal conductivity data for the resulting foam are shown in Table 3. This data (when compared with the data for Examples 13-16) indicates that foamable compositions of the present invention comprising unsaturated perfluorochemical blowing agent compound can provide foams having a smaller average cell size than foams prepared using 1,1-dichloro-l-fluoroethane and water as the sole blowing agents.
  • Polyurethane foams were prepared essentially according to the procedure of Example 1, using the components and amounts listed in Table 4. Pentane and water were used in each case as co-blowing agents. The density and thermal conductivity data for the resulting foams are shown in Table 4.
  • the density and thermal cond ⁇ ctivity data for the resulting foam are shown in Table 4.
  • foamable compositions of the present invention comprising unsaturated perfluorochemical blowing agent compound can provide foams having thermal conductivities superior to those of foam prepared using incompletely-fluorinated, unsaturated compounds such as that taught by Volkert et al. , supra.
  • a phenolic foam was prepared essentially as in Example 1 of European Pat. Publication No. 0 439 283 Al (BP Chemicals Limited) , except that HFP trimer (Hoechst AG) was substituted for the perfluoropentane.
  • HFP trimer Hoechst AG
  • the resulting foam was stable (no collapse) and had a large cell size.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Compositions expansibles contenant (a) au moins un composé d'agent moussant perfluoré non saturé liquide à température ambiante sélectionné dans le groupe formé de composés de perfluorooléfine tels que le perfluoro (4-méthylpent-2-ene), de composés perfluoroaromatiques, tels que l'hexafluorobenzène, et de composés de perfluorocyclooléfine, tels que le perfluorocyclohexène, lesdits composés de perfluorooléfine contenant facultativement au moins un hétéroatome caténaire, et (b) au moins un polymère expansible ou des précurseurs d'au moins un polymère expansible. Ces compositions sont utiles pour préparer des mousses polymères telles que des mousses de polyuréthane.
PCT/US1994/013095 1993-12-29 1994-11-16 Composition expansible contenant un agent moussant chimique perfluore non sature WO1995018176A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP51801995A JP3419779B2 (ja) 1993-12-29 1994-11-16 不飽和パーフルオロ化発泡剤を含有する発泡性組成物
EP95901889A EP0737223A1 (fr) 1993-12-29 1994-11-16 Composition expansible contenant un agent moussant chimique perfluore non sature

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/174,826 1993-12-29
US08/174,826 US5539008A (en) 1993-12-29 1993-12-29 Foamable composition containing unsaturated perfluorochemical blowing agent

Publications (1)

Publication Number Publication Date
WO1995018176A1 true WO1995018176A1 (fr) 1995-07-06

Family

ID=22637686

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/013095 WO1995018176A1 (fr) 1993-12-29 1994-11-16 Composition expansible contenant un agent moussant chimique perfluore non sature

Country Status (5)

Country Link
US (2) US5539008A (fr)
EP (1) EP0737223A1 (fr)
JP (1) JP3419779B2 (fr)
CA (1) CA2180251A1 (fr)
WO (1) WO1995018176A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6207725B1 (en) 1996-11-04 2001-03-27 Imperial Chemical Industries Plc Rigid polyurethane foams
US6403665B1 (en) 1996-11-04 2002-06-11 Imperial Chemical Industries Plc Rigid polyurethane foams
US8003708B2 (en) 2004-03-15 2011-08-23 Huntsman International Llc Process for making rigid polyurethane foams

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5401429A (en) * 1993-04-01 1995-03-28 Minnesota Mining And Manufacturing Company Azeotropic compositions containing perfluorinated cycloaminoether
KR0180613B1 (en) * 1994-09-07 1999-05-15 Matsushita Electric Ind Co Ltd Thermal insulating foamed material and method for manufacturing the same
WO2000070289A1 (fr) 1999-05-18 2000-11-23 3M Innovative Properties Company Transfert de chaleur en deux phases, sans degazage
US6610250B1 (en) 1999-08-23 2003-08-26 3M Innovative Properties Company Apparatus using halogenated organic fluids for heat transfer in low temperature processes requiring sterilization and methods therefor
US7022658B2 (en) * 2003-09-29 2006-04-04 3M Innovative Properties Company Azeotrope-like compositions containing hexafluoropropylene dimer and use thereof
DE602004007752T3 (de) † 2004-01-08 2015-06-18 Samsung Electronics Co., Ltd. Verfahren zur Herstellung von Polyurethan Hartschaumstoffen
US7691282B2 (en) * 2005-09-08 2010-04-06 3M Innovative Properties Company Hydrofluoroether compounds and processes for their preparation and use
US7790312B2 (en) * 2005-09-08 2010-09-07 3M Innovative Properties Company Electrolyte composition
AR058828A1 (es) * 2005-11-01 2008-02-27 Du Pont Agentes de expansion para formar espuma que comprenden fluorocarburos insaturados
US7385089B2 (en) * 2005-12-23 2008-06-10 3M Innovative Properties Company Fluorochemical ketone compounds and processes for their use
FR2899233B1 (fr) * 2006-03-31 2010-03-12 Arkema Composition d'agent d'expansion
US8791254B2 (en) * 2006-05-19 2014-07-29 3M Innovative Properties Company Cyclic hydrofluoroether compounds and processes for their preparation and use
US20100025619A1 (en) * 2006-07-12 2010-02-04 Solvay Fluor Gmbh Method for heating and cooling using fluoroether compounds, compositions suitable therefore and their use
US8193397B2 (en) * 2006-12-06 2012-06-05 3M Innovative Properties Company Hydrofluoroether compounds and processes for their preparation and use
ES2661884T3 (es) * 2007-11-29 2018-04-04 The Chemours Company Fc, Llc Composiciones y uso de una composición formadora de espuma cis-1,1,1,4,4,4-hexafluoro-2-buteno en la preparación de espumas a base de poliisocianato
EP2567992B1 (fr) * 2007-12-19 2015-11-04 E. I. du Pont de Nemours and Company Compositions moussantes contenant un mélange azéotropique ou de type azéotropique contenant du cis-1,1,1,4,4,4-hexafluoro-2-butène et du trans-1,2-dichloroethylène et leurs applications dans la préparation de mousses à base de polyisocyanate
US8071816B2 (en) * 2008-06-30 2011-12-06 3M Innovative Properties Company Hydrofluoroacetal compounds and processes for their preparation and use
US20110124758A1 (en) * 2008-08-13 2011-05-26 E.I. Du Pont De Nemours And Company Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and hydrocarbon and their uses in the preparation of polyisocyanate-based foams
US7988877B2 (en) * 2008-11-03 2011-08-02 3M Innovative Properties Company Methods of making fluorinated ethers, fluorinated ethers, and uses thereof
US8541478B2 (en) 2009-05-21 2013-09-24 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
US20110144216A1 (en) * 2009-12-16 2011-06-16 Honeywell International Inc. Compositions and uses of cis-1,1,1,4,4,4-hexafluoro-2-butene
EP2718253B1 (fr) 2011-06-10 2020-09-09 3M Innovative Properties Company Cétones partiellement fluorées et leurs procédés de fabrication et d'utilisation
US9896558B2 (en) * 2011-08-01 2018-02-20 Basf Se HFO/water-blown rigid foam systems
WO2015095285A1 (fr) 2013-12-20 2015-06-25 3M Innovative Properties Company Oléfines fluorées à utiliser en tant que fluides de travail et leurs procédés d'utilisation
CN112574387A (zh) * 2020-12-14 2021-03-30 长虹美菱股份有限公司 一种低成本环保型聚氨酯发泡料及其发泡工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03229732A (ja) * 1990-02-02 1991-10-11 Asahi Glass Co Ltd スチレン系樹脂発泡体の製造方法
JPH03229729A (ja) * 1990-02-06 1991-10-11 Asahi Glass Co Ltd ポリオレフィン発泡体の製造方法
JPH03229736A (ja) * 1990-02-06 1991-10-11 Asahi Glass Co Ltd フェノール樹脂発泡体の製造方法
EP0543536A1 (fr) * 1991-11-20 1993-05-26 Imperial Chemical Industries Plc Procédé pour des produits polymériques alvéolaires
JPH05168807A (ja) * 1991-12-20 1993-07-02 Daikin Ind Ltd ハロゲン化炭化水素組成物

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3331880A (en) * 1965-02-10 1967-07-18 Allied Chem Process for preparing polyfluorocyclohexenes
US4016217A (en) * 1965-04-08 1977-04-05 Imperial Chemical Industries Limited Preparation of perfluoroolefines
GB1296676A (fr) * 1969-03-03 1972-11-15
US3787351A (en) * 1972-02-28 1974-01-22 Minnesota Mining & Mfg Use of soluble fluoroaliphatic oligomers in resin composite articles
JPS5179045A (en) * 1974-12-26 1976-07-09 Moorisu Howaitosaido Piitaa Zairyokongoyunitsuto
JPS5179042A (ja) * 1974-12-28 1976-07-09 Ishikawajima Harima Heavy Ind Netsukokanki
JPS5179043A (fr) * 1974-12-30 1976-07-09 Eisuke Funakoshi
DE2638759A1 (de) * 1976-08-27 1978-03-09 Bayer Ag Loesungen von polyisocyanat-polyadditionsprodukten
DE2639084C2 (de) * 1976-08-31 1984-08-23 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Gemischen aus niedermolekularen Polyhydroxylverbindungen und ihre Verwendung zur Herstellung von Polyurethankunststoffen
DE2706297A1 (de) * 1977-02-15 1978-08-17 Bayer Ag Neue segmentierte polyurethankunststoffe
DE2714084A1 (de) * 1977-03-30 1978-10-12 Bayer Ag Verfahren zur herstellung von niedermolekularen polyhydroxylverbindungen
CA1088525A (fr) * 1977-03-30 1980-10-28 Kuno Wagner Procede d'obtention de composes de type polyhydroxyle a faible p.m.
US4221876A (en) * 1977-05-11 1980-09-09 Bayer Aktiengesellschaft Isocyanate-reactive mixtures based on formose
DE2738154A1 (de) * 1977-08-24 1979-03-08 Bayer Ag Verfahren zur herstellung von niedermolekularen polyhydroxylverbindungen
US4205138A (en) * 1977-08-26 1980-05-27 Bayer Aktiengesellschaft Polyurethane foams and elastomers prepared from low molecular weight polyhydroxyl compounds
JPS61252220A (ja) * 1985-04-30 1986-11-10 Dainippon Ink & Chem Inc ウレタン樹脂の製造方法
DE3824354A1 (de) * 1988-07-19 1990-01-25 Basf Ag Verfahren zur herstellung von zellhaltigen kunststoffen nach dem polyisocyanat-polyadditionsverfahren mittels lagerstabiler, treibmittelhaltiger emulsionen und diese emulsionen
US4972003A (en) * 1989-05-10 1990-11-20 The Dow Chemical Company Foaming system for rigid urethane and isocyanurate foams
US4981879A (en) * 1989-08-28 1991-01-01 Jim Walter Research Corp. Rigid foam with improved "K" factor from perfluorinated hydrocarbons
GB8919675D0 (en) * 1989-08-31 1989-10-11 Ici Plc Polymeric foams
US5120770A (en) * 1989-11-29 1992-06-09 Doyle Earl N Use of liquid carbon dioxide as a blowing agent in the production of open-cell polyurethane foam
GB9001368D0 (en) * 1990-01-20 1990-03-21 Bp Chem Int Ltd Blowing agents
US4997706A (en) * 1990-02-09 1991-03-05 The Dow Chemical Company Foaming system for closed-cell rigid polymer foam
DE4006952A1 (de) * 1990-03-06 1991-09-12 Hoechst Ag Verfahren zur herstellung von schaumstoffen mit hilfe von treibmitteln, die fluoralkane und fluorierte ether enthalten, sowie nach diesem verfahren erhaeltliche schaumstoffe
US5220082A (en) * 1990-10-11 1993-06-15 E. I. Du Pont De Nemours And Company Process for production of polyfluoroolefins
US5240965A (en) * 1991-04-03 1993-08-31 Imperial Chemical Industries Plc Manufacture of cellular polymers and compositions therefor
US5238970A (en) * 1991-04-03 1993-08-24 Imperial Chemical Industries, Plc Manufacture of rigid foams and compositions therefor
US5356556A (en) * 1991-04-03 1994-10-18 Imperial Chemical Industries Plc Manufacture of rigid foams and compositions therefor
DE4119459A1 (de) * 1991-06-13 1992-12-17 Basf Ag Verfahren zur herstellung von zellhaltigen kunststoffen nach dem polyisocyanat-polyadditionsverfahren und niedrigsiedende, fluorierte und/oder perfluorierte, tertiaere alkylamine als treibmittel enthaltende emulsionen hierfuer
US5137929A (en) * 1991-06-21 1992-08-11 Allied-Signal Inc. Additives which stabilize hydrohalocarbon blowing agent in polyurethane and polyisocyanurate foam formulations during polymerization
DE4121161A1 (de) * 1991-06-27 1993-01-07 Basf Ag Verfahren zur herstellung von urethan- oder urethan- und isocyanuratgruppen enthaltenden hartschaumstoffen und treibmittel enthaltende emulsionen hierfuer
FR2678279B1 (fr) * 1991-06-27 1993-09-03 Atochem Application de (perfluoroalkyl)-ethylenes comme agents d'expansion et/ou gaz d'isolation pour mousses de polymeres.
US5162384A (en) * 1991-09-13 1992-11-10 Minnesota Mining And Manufacturing Company Making foamed plastic containing perfluorinated heterocyclic blowing agent
US5210106A (en) * 1991-10-04 1993-05-11 Minnesota Mining And Manufacturing Company Fine-celled plastic foam containing fluorochemical blowing agent
US5211873A (en) * 1991-10-04 1993-05-18 Minnesota Mining And Manufacturing Company Fine-celled plastic foam containing fluorochemical blowing agent
JPH05247249A (ja) * 1991-11-27 1993-09-24 Daikin Ind Ltd 発泡剤およびプラスチック発泡体の製造方法
US5254774A (en) * 1992-12-28 1993-10-19 Minnesota Mining And Manufacturing Company Preparation of hexafluoropropene oligomers
DE69324784T2 (de) * 1992-12-30 1999-10-21 Ici Plc Verfahren zur Herstellung von Hartschaumstoffen
US5346928A (en) * 1993-09-09 1994-09-13 Imperial Chemical Industries Plc Rigid polyurethane foams
US5318996A (en) * 1993-10-08 1994-06-07 Basf Corporation Rigid insulating polyurethane foams prepared from ternary blowing agent mixtures

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03229732A (ja) * 1990-02-02 1991-10-11 Asahi Glass Co Ltd スチレン系樹脂発泡体の製造方法
JPH03229729A (ja) * 1990-02-06 1991-10-11 Asahi Glass Co Ltd ポリオレフィン発泡体の製造方法
JPH03229736A (ja) * 1990-02-06 1991-10-11 Asahi Glass Co Ltd フェノール樹脂発泡体の製造方法
EP0543536A1 (fr) * 1991-11-20 1993-05-26 Imperial Chemical Industries Plc Procédé pour des produits polymériques alvéolaires
JPH05168807A (ja) * 1991-12-20 1993-07-02 Daikin Ind Ltd ハロゲン化炭化水素組成物

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9147, Derwent World Patents Index; AN 91-343658, "Prodn of polyolefin foam" *
DATABASE WPI Week 9147, Derwent World Patents Index; AN 91-343661, "Prodn. of styrene resin foam." *
DATABASE WPI Week 9147, Derwent World Patents Index; AN 91-343665, "Prepn. of foamed phenol. resin product" *
DATABASE WPI Week 9331, Derwent World Patents Index; AN 93-247652, "Halogenated hydrocarbon composition" *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6207725B1 (en) 1996-11-04 2001-03-27 Imperial Chemical Industries Plc Rigid polyurethane foams
US6346205B2 (en) 1996-11-04 2002-02-12 Huntsman International Llc Rigid polyurethane foams
US6403665B1 (en) 1996-11-04 2002-06-11 Imperial Chemical Industries Plc Rigid polyurethane foams
US6528549B2 (en) 1996-11-04 2003-03-04 Imperial Chemical Industries Plc Rigid polyurethane foams
US8003708B2 (en) 2004-03-15 2011-08-23 Huntsman International Llc Process for making rigid polyurethane foams

Also Published As

Publication number Publication date
CA2180251A1 (fr) 1995-07-06
EP0737223A1 (fr) 1996-10-16
JPH09507258A (ja) 1997-07-22
US5631306A (en) 1997-05-20
US5539008A (en) 1996-07-23
JP3419779B2 (ja) 2003-06-23

Similar Documents

Publication Publication Date Title
US5631306A (en) Foamable composition containing unsaturated perfluorochemical blowing agent
US7763578B2 (en) Preparation of polymeric foams using hydrofluoroether nucleating agents
US5210106A (en) Fine-celled plastic foam containing fluorochemical blowing agent
US5278195A (en) Production of plastic foams, preferably rigid foams containing urethane groups or urethane and isocyanurate groups, and blowing agent-containing emulsions for this purpose
US5211873A (en) Fine-celled plastic foam containing fluorochemical blowing agent
KR100629811B1 (ko) 플루오르화된 케톤을 발포제로서 사용하는 중합체 폼 제조방법
US5162384A (en) Making foamed plastic containing perfluorinated heterocyclic blowing agent
US20140058003A1 (en) Polymeric foams including fluorinated oxiranes, methods of preparation, and use of same
CA2217988C (fr) Mousses rigides ayant des proprietes insolantes ameliorees et procede pour leur production
MXPA97007792A (es) Espumas rigidas con mejores propiedades deaislamiento y un procedimiento para la produccionde dichas espumas
CA2343689A1 (fr) Methode de preparation d'une mousse polymerique a l'aide d'un compose chimique perfluore dissous ou disperse dans un hydrofluoroether
MXPA97002554A (en) Rigi polyurethane foams
JPH05279653A (ja) ポリマーフォーム用の発泡剤及び／または断熱ガスとしての（ペルフルオロアルキル）エチレンの適用
WO1996037540A1 (fr) Composition expansible contenant un agent gonflant perfluorochimique insature
DE4143148B4 (de) Verfahren zur Herstellung von zellhaltigen Kunststoffen nach dem Polyisocyanat-Polyadditionsverfahren und Treibmittelmischungen enthaltende Emulsionen hierfür
KR20010080903A (ko) 히드로플루오로에테르 중에 용해 또는 분산된퍼플루오르화합물을 사용하는 중합체 폼 제조 방법

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995901889

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2180251

Country of ref document: CA

WWP Wipo information: published in national office

Ref document number: 1995901889

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1995901889

Country of ref document: EP